Integral composite structure incorporating multiple resin-based systems and method of manufacture

ABSTRACT

A composite structure is provided. The structure is based upon a three-dimensional woven fabric structure. The three-dimensional woven fabric has a first fabric layer and a second fabric layer spaced apart from the first fabric layer, with the layers connected by threads which form a portion of the three-dimensional woven fabric structure. The threads define voids in the space between the first and second layers. A first resinous material is coated onto and allowed to penetrate the first layer of the woven fabric structure. Next a second resinous material is coated onto and allowed to penetrate the second layer of the woven fabric structure. Following the application of the resins, the voids remain substantially empty. In order to complete the formation of the composite structure, the resins are fully cured. Using this method it is possible for the first resinous material and the second resinous material to be chemically incompatible, yet mechanically attached by the cloth material.

BACKGROUND

1. The Field of the Invention

The present invention is related to structures which incorporatemultiple resin systems yet which are mechanically integral. Moreparticularly, the present invention relates to structures and methodswhich are capable of incorporating chemically dissimilar resins within asingle integral structure by means of a three-dimensional cloth.

2. Technical Background

Laminated composite structures are used in many different environments.Such structures are often referred to by the generic designationfiberglass. Structures of this type are generally composed of layers ofa polymeric resin along with some type of supporting structure. Thesupporting structure is often a fibrous material of various types. Awide variety of products are produced using these types of materials.For example, most conventional boats are constructed of these types ofmaterials. Other similar products include rail transportation cars, carbodies, consumer products, some types of building materials, andcomponents for larger structures.

In order to achieve a desired balance of physical, chemical, andmechanical characteristics within the structure, it is often necessaryto layer materials. For example, it is not uncommon to include a layerof structurally strong material with a layer of material that may not beas strong but which provides an attractive finish. Similarly, it isoften desirable to provide a layer of material that can act as a firebreak in combination with other materials. As a result, the overallstructure may include a plurality of layers including structuralmaterials, fire breaks, and finish layers. In this way it is possible totake advantage of the structural features of a strong structuralmaterial, while still producing an attractive end product, or one whichis not prone to ignition during a fire.

In general, such structures often incorporate three or more separatelayers having distinct mechanical and chemical characteristics. Atypical example may include a gel coat which results in an attractivefinish, a fibrous mat, a structural conglomerate layer which includes aquantity of fibers, and a more solid backing layer.

One of the difficulties encountered in manufacturing this type ofstructure relates to bonding multiple layers together to form a singlestructure. In most cases, adhesives are used to bond the layerstogether. Thus, the final product results in layers of adhesivesinterposed between each of the structural layers.

When materials are layered in this manner several problems are observed.For example, when layers are bonded together with adhesive it is notuncommon for the layers to separate. This is especially prevalent instructures which are subjected to very rigorous environments, such asboats and other vehicles. When the layers separate, "delamination" isobserved. This phenomenon is clearly disadvantageous. At the least, thestructure looses its attractive finish. At worst, the structure is nolonger structurally sound or useful.

Alternatively, the layer may be held together with mechanical fastenerssuch as bolts, rivets, screws, and the like. There are obvious problemswith this type of attachment. Since the mechanical fasteners aregenerally much harder than the composite materials, the composites havea tendency to wear in the area of the mechanical fastener. Thus, thelayered material will eventually fail because of wear between themechanical fastener and the composite.

Problems with attachment of layers of composite materials isparticularly acute when chemically incompatible resins systems are used.Chemically incompatible materials can generally be defined as materialsthat will not significantly cross-link during curing. In such cases itis clearly necessary to bond the two systems together mechanically orwith an adhesive because chemical interaction between the layersthemselves is not possible. Yet it may be difficult to achieve adequatebonding using a single adhesive due to the characteristics of the resinsused. In addition, it is difficult to achieve an adhesive bond that isas strong as the remainder of the structure. As a result, failure of thebonded area is often observed.

Thus, it would be desirable to bond certain types of chemicallyincompatible systems together in layered composite structures withoutusing mechanical connections or adhesives of the type described above.For example, polyester systems can be made to be cosmeticallyattractive, but often lack the desired strength to form a structuralcomponent. At the same time, epoxy systems are known to be strong, yetmay lack the desired appearance. Thus, it may be desirable to bond apolyester system to an epoxy system in order to achieve structuralintegrity and an attractive appearance. In the past this approach hashad limited success because these materials are generally chemicallyincompatible and chemical bonding is problematic at best.

Similarly, as mentioned briefly above, it is at times necessary toprovide a flame and smoke barrier in a laminated structure. In thosecases it would be helpful to include a layer of a phenolic-based resinsystem. Phenolics are known for their ability to resist combustion. Itmay be desirable, for example, to combine these features with thestrength of an epoxy system. Again, however, phenolics and epoxies arenot chemically compatible and must be bonded together by the use ofadhesive or mechanical fasteners.

Accordingly, it would be a significant advancement in the art to providemethods for joining two or more resin systems into an integral structurewithout the necessity of adhesives, mechanical fasteners, or otherconventional joining methods. It would be a related advancement toprovide means for joining materials with different desirablecharacteristics, while substantially avoiding the possibility ofdelamination of the material. In that regard, it would be useful to havemeans for joining two chemically incompatible resin-systems without theneed to employ adhesives and the like.

Such methods and structures are disclosed and claimed herein.

BRIEF SUMMARY AND OBJECTS OF THE INVENTION

The present invention is related to structures which incorporatemultiple resin systems in a mechanically integral manner. The term"integral" as used herein refers to a structure which is formed withoutthe need for the use of adhesives, mechanical fasteners, or other typesof conventional bonding of methods. Rather, the integral structure ofthe present invention, when completed, is a single unitary structurewhich is internally bound together.

Using the methods of the present invention it is possible to providestructures which are capable of incorporating chemically dissimilarsynthetic resins within a single integral structure. The presentinvention employs a three-dimensional woven fabric structure. The fabricstructure has a first fabric layer and a second fabric layer spacedapart from the first fabric layer. The first and second layers areconnected by woven intermediate fibers which form a portion of thethree-dimensional woven fabric structure. In addition to connecting thefirst and second fabric layers, the intermediate fibers define aplurality of voids in the space between the first and second layers.This type of fabric is sometimes referred to in the art as an"integrated sandwich structure."

Three-dimensional woven fabric of this general type are commerciallyavailable. Examples of this type of fabric include Parabeam®three-dimensional glass fabric available from Parabeam, a member ofGamma Holding Nederland N.V., Helmond, Netherlands. Similar products areavailable from Vorwerk & Co. Mobelstoffwerke GmbH & Co. KG, Kulmbach,Germany.

The three-dimensional glass fabric is then contacted with a firstresinous material. This material is likely to constitute a conventionalresin such as a polyester resin, vinylester resin, phenolic resin, orepoxy resin. Any one of a substantial number of resins and combinationsof resins may be used in the context of the present invention. Resins ofthis type are well known in the materials art and are commerciallyavailable.

The first resin is allowed to penetrate the first layer of the wovenfabric structure. As the resin penetrates the first layer of the wovenfabric structure, the resin "wicks" up the intermediate fibers. However,care is taken to assure that the resin does not fill the voids in theareas between the two fabric layers. The three dimensional glass fabricprovides this capability in that the resin wicks up the threads ratherthan filling the voids in the material. In that regard it is observedthat the resin tends not to fill the voids unless extraordinary stepsare taken to force the resin into the voids.

At this point, a second resinous material is allowed to penetrate thesecond layer of the woven fabric structure. The second resin also wicksup the intermediate fibers threads, but does not substantially overlapthe first resin. Thus, the resulting structure is comprised of a firstresin system penetrating the first woven fabric layer; a second resinsystem (which is potentially chemically incompatible with the firstsystem) penetrating the second woven fabric layer; and the resin systemswicking up the joining intermediate fibers, but not substantiallyfilling the voids in the fabric. Finally, the two resin systems arecured by conventional means, resulting in a single integral structure.

Thus, an "integral" structure is provided in that there is no necessityof joining layers together by adhesives or with conventional mechanicalfasteners. Rather, the combination of the woven fabric fibers and thecured resin systems result in a complete, sound structure. The singleintegral structure comprises at least two resin systems mechanically(not necessarily chemically) bonded together by means of the wovenfibers of the fabric.

BRIEF DESCRIPTION OF THE DRAWINGS

In order to more fully understand the manner in which the above-recitedand other advantages and objects of the invention are obtained, a moreparticular description of the invention briefly described above will berendered by reference to specific embodiments thereof which areillustrated in the appended drawings. Understanding that these drawingsdepict only typical embodiments of the invention and are not thereforeto be considered limiting of its scope, the invention will be describedand explained with additional specificity and detail through the use ofthe accompanying drawings in which:

FIG. 1 is a perspective view of one embodiment of the present invention.

FIG. 2 is a perspective view of the three-dimensional woven fabric ofthe present invention.

FIG. 3a is a cross sectional view of a section of three dimensionalwoven fabric and a first resin system.

FIG. 3b is a cross sectional view of the first layer of the section offabric shown in FIG. 3a being placed into the first resin system.

FIG. 3c is a cross sectional view of the first resin system wicking upthe intermediate fibers in the three dimensional woven fabric.

FIG. 4a is a cross sectional view of the woven fabric of FIGS. 3a-3c,with the second layer being positioned with respect to a second resinsystem.

FIG. 4b is a cross sectional view of the woven fabric of FIG. 4a beingplaced into the second resin system.

FIG. 4c is a cross sectional view of the second resin system wicking upthe intermediate fibers of the woven fabric.

FIG. 5 is a cross sectional view of a completed integral structurewithin the scope of the invention having a first and second resin systembonded together by means of the intermediate fibers of the fabric.

FIG. 6 is a cross sectional view illustrating a structure having threefabric layers and three separate resin systems bonded together.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

The present invention can be best understood by reference to thedrawings where like parts are designated with like numerals throughout.The present invention is related to integral composite structures formedusing three-dimensional woven fabric and one or more resin systems. Asmentioned above, the three-dimensional woven fabric is commerciallyavailable and may be obtained from multiple suppliers includingParabeam, a member of Gamma Holding Nederland N.V., Helmond, Netherlandsand Vorwerk & Co. Mobelstoffwerke GmbH & Co. KG, Kulmbach Germany.

The structure of a typical three-dimensional woven fabric of the typeused in the present invention is illustrated in FIG. 2 and generallydesignated 10. Generally, the fabric will be a glass fabric, however,other materials may also be acceptable in certain applications. Othermaterials that may include, for example, carbon, graphite, silicon,carbide, boron, polyaramide, polyester, polyamide, rayon,polybenxinidazole, polybenzothiozole, or a metallic coated fiber orcombinations thereof.

The fabric is woven such that it essentially forms a first bottom fabriclayer 12 and a second top fabric layer 14. The layers are formed by theweave of the fibers which form the fabric. The first layer 12 and thesecond layer 14 are connected by intermediate vertical fibers 16. Thetwo layers are generally standard fabrics spread in the warp and weftdirections.

In one preferred embodiment, the fabric is a woven glass fiber fabrichaving a density of 280 g/m², although densities up to 2500 g/m² arecommercially available. In one embodiment, the fabric has a thickness of6 mm, and in the warp direction there are channels or voids 18 which are4 mm wide. In the weft direction there are two intermediate (vertical)fibers 16 per millimeter.

The fabric illustrated in FIG. 2 is used in the methods of the presentinvention to produce the novel integral composite structures of thepresent invention. One embodiment of such a structure is illustrated inFIG. 1 and generally designed 20. The structure 20 is comprised of thewoven fabric 10 illustrated in FIG. 2 which forms the structuralfoundation of the material.

The woven fabric 10 is then contacted with a first resin system suchthat a first (bottom) layer 12 of the fabric is saturated by resin. Careis taken such that the voids 18 in the fabric structure do not fill withresin. Rather the resin is allowed to "wick" up the intermediate fibers16. The process is then repeated on the second (top) fabric layer 14 andthe overall structure is cured. The final product is an integralcomposite structure comprising a first resin system 22 cured over thebottom fabric layer 12 and a second resin system 24 cured over the topfabric layer 14. While the first and second resin systems are allowed towick up the intermediate fibers 16, the voids 18 remain empty in thefinal product.

The processes of the present invention can be more fully appreciatedwith reference to FIGS. 3a-3c and FIGS. 4a-4c. In FIG. 3a the fabric 10of FIG. 2 is once again observed. The structure of the first bottomlayer 12 and the second top layer 14 can be more fully appreciated withreference to FIG. 3a. It can be seen that the woven fibers of the fabric10 combine to produce the two spaced apart fabric layers. As previouslydiscussed, the fabric layers are integrally joined together by the wovenvertical intermediate fibers 16. The structure also results in aplurality of voids 18 disposed between the fabric layers 12 and 14 andfurther defined by the intermediate fibers 16.

Also illustrated in FIG. 3a is a quantity of a first resin system 26 inun-cured liquid form. The first resin 26 may include any one of a largenumber of known resin materials. Typical examples of such resins includepolyesters, vinylesters, epoxies, and phenolic resins. Specific examplesof resins of the type usable within the scope of the present inventioninclude: polyesters manufactured by Shell, Ashland, Reichold; epoxiesmanufactured by Shell, Reichold, Ashland; vinylesters manufactured byInterplastics, Ashland; and phenolics manufactured by British Petroleum.

The steps in the process during which curing occurs will be discussed inadditional detail below. However, it is notable that conventional curingmethods are used. Curing may include the addition of a chemical curingagent to initiate cure, or in some cases curing will be initiated bylight or heat. With regard to the major categories of resins set forthabove (i.e. polyesters, vinylesters, epoxies, and phenolic resins)curing is typically accomplished by the following mechanism(s):

Polyesters: Catalyst; Epoxies: Catalyst, Catalyst & Heat; Vinylesters:Catalyst; Phenolics: Catalyst & Heat.

Once the resin 26 and the woven fabric 10 are prepared, a first layer 12of the fabric is placed into contact with the liquid resin. This step inthe process is illustrated in FIG. 3b. The resin can be rolled onto thefabric, or the fabric may be dipped into the resin. Either way, it isonly necessary that the resin thoroughly saturate the first layer 12 ofthe fabric.

Following saturation of the first layer 12 by the resin 26, the resin istypically allowed to wick up the intermediate vertical fibers 16. FIG.3c illustrates the manner in which this occurs. As mentioned above,however, it is observed that the resin does not tend to fill the voids18 in the fabric. In addition, the resin generally tends to travel onlya portion of the length of the intermediate vertical fibers 18.

At this point in the process the first resin is either cured or furtherstabilized in order to accommodate the completion of the further stepsin the process.

The remaining steps in the basic process are illustrated in FIGS. 4a-4c.FIG. 4a illustrates the woven fabric 10 with the first layer 12 of thefabric encased in the stabilized (or cured) first resin 26. Alsoillustrated in FIG. 4a is a second liquid resin 28. The second (top)layer 14 of the woven fabric 10 is positioned such that it is preparedto contact the second resin 28.

FIG. 4b illustrates the second layer 14 being placed into contact withthe second resin 28. This takes place in the same manner as describedabove with reference to FIG. 3b. In particular, the second resin 28 isallowed to thoroughly penetrate the second layer 14.

As illustrated in FIG. 4c, the second resin is generally allowed to wickup the intermediate vertical fibers 16 until it comes into contact withthe first resin at a junction 30. In this manner the fabric 10 issubstantially encased within the two resin systems.

Once the coating process shown in FIG. 4c is completed, the second resinis cured and the curing of the first resin is completed if necessary.The final product is illustrated in FIG. 5. With reference to FIG. 5 itwill be appreciated that the first layer 12 is coated and encased withinthe first resin system 26. The first resin system 26 extends up theintermediate vertical fibers to the junction 30. At the same time thesecond layer 14 is encased within the second resin system 28, while thesecond resin system extends down the intermediate fibers 16 to thejunction 30. Thus, the woven fabric 10 is substantially encased inresin, even though there is not necessarily any chemical interactionbetween the two resin systems at the junction 30.

The result of the process is an integral composite structure as thatterm is defined herein. This is the case even in the event the two resinsystems are chemically incompatible. Specifically, the two layers 12 and14 are linked together by the woven intermediate fibers 16. Thisprovides a strong link between the two cured resins systems such that astrong integral composite is produced.

FIG. 6 is an alternative embodiment of the present invention. It will beappreciated that it is possible, using the present invention, to preparemultiple layer materials such that all of the layers are integral,within the meaning of that term as used herein. In forming such astructure it is possible to use two, or more, sheets ofthree-dimensional woven fabric. Alternatively, a single three layermaterial may be used. The result is three spaced apart fabric layersdesignated 36, 38, and 40 in FIG. 6.

As illustrated in FIG. 6, the fabric layers are encased into threeseparate resin systems. Fabric layer 36 is covered by a resin system 42.That system extends down the intermediate vertical fibers 44 to ajunction 46 with a second resin system 48. The second resin system 48encases the second fabric layer 38 and extends down the intermediatevertical fibers 44 to a second junction 50. At junction 50 the secondresin system meets a third resin system 52. The third resin system 52then cases the third fabric layer 40. Once each of the resin systemsillustrated in FIG. 6 is fully cured, a strong integral structure isformed.

It will be appreciated that the present invention has a number ofapplications. As mentioned above, it is often desirable to incorporatethe characteristics of multiple resin systems into a single structure.However, problems often arise in bonding the various layers together,particularly if the resin systems are chemically incompatible. Thus, thepresent invention provides means for bonding together chemicallyincompatible resin systems in a manner that still has structuralintegrity.

Materials of this type have a wide array of applications. As mentionedabove, such materials are useful in the manufacture of boats, train andsubway cars, and other similar vehicles of transportation. In addition,these types of materials have application in modular building materials.In that regard, one of the benefits of this type of material is thatwiring and other utilities can often be guided through the voids 18 inthe structure. Furthermore, the multiple layer construction, with deadair space in the center, provides excellent sound and thermalinsulation.

EXAMPLE

The following example is given to illustrate various embodiments whichhave been made or may be made in accordance with the present invention.This example is given by way of example only, and it is to be understoodthat the following example is not comprehensive or exhaustive of themany types of embodiments of the present invention which can be preparedin accordance with the present invention.

Example 1

A material within the scope of the present invention was made by thefollowing steps:

This sample laminate consists of three layers of 1/4" Parabeam, with thefirst layer being saturated with British Petroleum's J2027L PhenolicResin. The third layer is saturated with Shell's 826 Epoxy Resin. Thecenter layer is a combination of the two resin systems.

The first 1/4" layer of Parabeam is placed on a plate and saturated withBritish Petroleum's J2027L Phenolic Resin combined with Phencat 10catalyst at 8% by weight. The second layer of 1/4" Parabeam is placed onthe first layer and partially saturated until the connecting fibers arecoated with resin approximately half their length. The lay-up is thenplaced in the oven to cure for approximately one hour or until a uniformpink color is achieved at 180° F.

After cooling, the second layer of Parabeam is then saturated the restof the way with Shell's 826 Epoxy resin combined with 2167 Pacm Hardenerby Pacific Anchor at 29% by weight. The third layer of 1/4" Parabeam isplaced on the laminate and saturated completely with the same epoxyresin system. A caul plate is placed over the lay-up to control thesurface finish and the part thickness. The lay-up is then placed in anoven the cure for approximately 2 hours at 180° F. This also acts as apost-cure for the Phenolic Resin.

The laminate is finally removed from the oven, de-molded, and trimmed tofinal size.

SUMMARY

The present invention represents a significant advancement in the art inthat it provides methods for joining two or more resin systems into anintegral structure without the necessity of adhesives, mechanicalfasteners, or other conventional joining methods. The present inventionprovides means for joining materials with different desirablecharacteristics, while substantially avoiding the possibility ofdelamination of the material. In that regard, the present inventionprovides means for joining two chemically incompatible resin-systemswithout the need to employ adhesives and the like.

The invention may be embodied in other specific forms without departingfrom its spirit or essential characteristics. The described embodimentsare to be considered in all respects only as illustrative and notrestrictive. The scope of the invention is, therefore, indicated by theappended claims rather than by the foregoing description. All changeswhich come within the meaning and range of equivalency of the claims areto be embraced within their scope.

What is claimed is:
 1. A composite structure comprising:athree-dimensional woven fabric structure having a first fabric layer anda second fabric layer spaced apart from the first fabric layer, saidlayers connected by intermediate fibers forming a portion of thethree-dimensional woven fabric structure, said fibers defining voids inthe space between the first and second layers; a first cured resinousmaterial penetrating the first layer of the woven fabric structure; asecond cured resinous material, said second resinous material comprisinga resin different from said first resinous material, said secondresinous material penetrating the second layer of the woven fabricstructure.
 2. A composite structure as defined in claim 1 wherein thevoids remain substantially empty.
 3. A composite structure as defined inclaim 1 wherein the first resinous material and the second resinousmaterial are chemically incompatible.
 4. A composite structure asdefined in claim 1 wherein said three-dimensional woven fabric comprisesa woven glass material.
 5. A composite structure as defined in claim 1wherein said three-dimensional woven fabric is constructed of materialsselected from the group consisting of carbon, graphite, silicon,carbide, boron, polyaramide, polyester, polyamide, rayon,polybenxinidazole, polybenzothiozole, a metallic coated fiber andcombinations thereof.
 6. A composite structure as defined in claim 1wherein one of the resinous materials is a polyester-based resin.
 7. Acomposite structure as defined in claim 1 wherein one of the resinousmaterials is an epoxy-based resin.
 8. A composite structure as definedin claim 1 wherein one of the resinous materials is a phenolic-basedresin.
 9. A composite structure as defined in claim 1 wherein theresinous materials are selected from the group consisting of polyesters,epoxies, phenolics, and vinylester.
 10. A composite structurecomprising:a three-dimensional woven fabric structure having a firstfabric layer and a second fabric layer spaced apart from the firstfabric layer, said layers connected by intermediate fibers forming aportion of the three-dimensional woven fabric structure, said fibersdefining voids in the space between the first and second layers; a firstcured resinous material penetrating the first layer of the woven fabricstructure; a second cured resinous material penetrating the second layerof the woven fabric structure; wherein the first resinous material andthe second resinous material are chemically incompatible; and whereinsaid first and second cured resinous materials also cover at least aportion of the intermediate fibers and meet, but do not substantiallyoverlap, to form a resin interface at a junction point on said fibers.11. A composite structure as defined in claim 10 wherein the first andsecond resinous materials are not chemically bonded together at the theresin interface.
 12. A composite structure as defined in claim 10wherein said woven fabric structure comprise woven glass fiber.
 13. Acomposite structure as defined in claim 10 wherein said first resinousmaterial is selected from the group consisting of epoxy resins, phenolicresins, polyester resins, and vinylester resins.
 14. A compositestructure as defined in claim 10 wherein said second resinous materialis selected from the group consisting of epoxy resins, phenolic resins,polyester resins, and vinylester resins.
 15. A process for preparing acomposite structure comprising the steps of:obtaining athree-dimensional woven fabric structure having a first fabric layer anda second fabric layer spaced apart from the first fabric layer, saidlayers connected by threads forming a portion of the three-dimensionalwoven fabric structure, said threads defining voids in the space betweenthe first and second layers; placing said first layer in contact with afirst resinous material and allowing the first resinous material topenetrate the first layer of the woven fabric structure; placing saidsecond layer in contact with a second resinous material, where saidsecond resinous material is different from said first resinous material,and allowing the second resinous material to penetrate the second layerof the woven fabric structure; and curing said first and second resinousmaterials.
 16. A process as defined in claim 15 wherein said first andsecond resinous materials are allowed to wick up said threads whichdefine said voids.
 17. A process as defined in claim 16 wherein saidfirst and second resinous materials meet at a junction point on saidintermediate fibers to form a resin interface and the first and secondresinous materials are not chemically bonded together at the resininterface.
 18. A process as defined in claim 15 wherein saidthree-dimensional woven fabric comprises a woven glass material.
 19. Aprocess as defined in claim 15 wherein said three-dimensional wovenfabric is constructed of materials selected from the group consisting ofcarbon, graphite, silicon, carbide, boron, polyaramide, polyester,polyamide, rayon, polybenxinidazole, polybenzothiozole, a metalliccoated fiber and combinations thereof.
 20. A process as defined in claim15 wherein one of the resinous materials is a polyester-based resin. 21.A process a defined in claim 15 wherein one of the resinous materials isan epoxy-based resin.
 22. A process as defined in claim 15 wherein oneof the resinous materials is a phenolic-based resin.
 23. A process asdefined in claim 15 wherein the resinous materials are selected from thegroup consisting of polyesters, epoxies, phenolics, and vinylester. 24.A process as defined in claim 15 wherein the voids are substantiallyempty.